1. Field of the Invention
The present invention relates to the production of supported noble metal alloy catalysts for use in fuel cell electrodes and other catalytic structures.
2. Description of the Prior Art
A fuel cell is a device which converts the energy of a chemical reaction between a fuel and oxidant directly into low voltage, direct current electricity. The problems encountered in obtaining an efficient fuel cell are essentially those of chemical kinetics. It is necessary that the reactions of the fuel and oxidant occur in such manner that the amount of energy degraded into heat is as small as possible. At the same time, the reaction rate of the cell must be high enough to produce economically sufficient current from a cell of practical size. For this reason it is customary to incorporate catalysts in the fuel cell which accelerate the reactions occurring at the electrodes.
A typical fuel cell comprises a fuel electrode or anode, an oxidant electrode or cathode, an electrolyte positioned between the electrodes and means to introduce fuel and oxidant to their respective electrodes. Each electrode is typically comprised of a substrate (such as wetproofed paper made from graphitized carbon fibers) with a layer of catalyst disposed on the surface which faces the electrolyte.
In operation, the fuel (commonly hydrogen) is fed to the anode where it is oxidized at the catalytic surface in the presence of electrolyte with the liberation of electrons. Simultaneously oxygen (or air) is fed to the cathode where it is reduced at a catalytic surface in the presence of electrolyte with the consumption of electrons. The electrons generated at the anode are conducted to the cathode through wires external to the cell and constitute a flow of electrical current which can be made to perform useful work.
To obtain fuel cells which are practical on a commercial scale, a great deal of research has been carried out in an effort to find improved catalysts. For example, the prior art has demonstrated that the activity per unit mass of a catalyst, usually a noble metal, can be enhanced by supporting it in the form of finely divided particles, upon either metallic or carbonaceous base materials of high surface area. This approach has proved especially useful in fuel cell applications utilizing acid electrolytes, for example, where particulate platinum is highly dispersed on a conductive support material such as carbon black and the platinum-covered carbon black, mixed with a suitable bonding agent, is applied as a thin layer on a conductive carbon paper or cloth to form an electrode.
In addition, the prior art has demonstrated that certain unsupported noble metal alloy catalysts exhibit increased catalytic activity and/or increased resistance to sintering and dissolution in fuel cells and other electrochemical and chemical processes when compared to the performance of the unalloyed noble metal catalyst. For example, U.S. Pat. No. 3,506,494 describes a method for producing a ternary alloy for use at the anode of a fuel cell. The ternary alloy consists of platinum, ruthenium and a metal selected from the following: gold, rhenium, tantalum, tungsten, molybdenum, silver, rhodium, osmium, or iridium. Although it states in column 3, at lines 67-70, that the alloy catalysts may be dispersed on a high surface area carrier such as carbon powder, no method is taught for doing this.
U.S. Pat. No. 3,428,490 describes another method for making a fuel cell anode electrode. In this case unsupported platinum is alloyed with aluminum and applied to an electrode substrate. The aluminum is then leached out to the extent possible to form the finished electrode. The removal of the aluminum produces a large number of reaction sites or voids in the electrode. It is stated that the voids increase the surface area and thus the activity of the catalyst. Although this patent indicates in column 6 at lines 26-29 that some aluminum may still be present in the electrode composition after leaching, it is believed that the amount remaining is not significant and it would be present only in those areas which could not be reached by the leaching solution. The patent teaches no method for making a noble metal-aluminum alloy which is supported.
Patents of more general interest which relate to platinum alloy catalysts are U.S. Pat. Nos. 3,340,097 (platinum-tin-ruthenium) and 3,615,836.
It is known that some alloys may be made by co-reducing intimate mixtures of reduceable metal salts. For example, the method of co-reducing metal salts in the presence of a support material is used to make a supported, finely divided platinum-iron alloy as explained in an article by C. Bartholomew and M. Boudart titled "Preparation of a Well Dispersed Platinum-Iron Alloy on Carbon" from the Journal of Catalysis, pp. 173-176, V25, #1, April 1972. However, salts of certain metals are not readily reduced. Such metals are those which form refractory metal oxides, e.g., Ti, Ce, Mg, Al, Si, and Ca.
It is apparent from the foregoing that there is still no commercially viable process for preparing high surface area catalysts of noble metals alloyed with the metallic component of a refractory metal oxide. It has been observed, however, that platinum and other noble metals and noble metal alloys, in bulk form, react with many refractory metal oxides at high temperatures to form solid solution alloys or intermetallic alloy compounds and that these reactions are accelerated by the presence of reducing agents in the high temperature environment of, for example, carbon, hydrogen, carbon monoxide and certain organic vapors. "Platinum Metals Review 20," No. 3, p. 79, July 1976.
Finally, returning to the subject of fuel cells, all base metals, including the refractory metals, are notoriously susceptible to oxidation and dissolution at cathodes in acid fuel cells, and it is not believed that alloys of noble metals with base metals have ever been considered for use at cathodes for that very reason, whether supported or unsupported.
As used herein, "noble metals" refers to those metals of the second and third triads of Group VIII of the Periodic Table, also referred to as the palladium and platinum groups, respectively. These metals are ruthenium, rhodium, palladium and osmium, iridium and platinum.